JP2018146960A - Cold pressure fixing toner composition and process - Google Patents

Abstract

Cold pressure fixing (CPF) toner can fix toner on paper without heating. To provide a cold-fixing toner that can be fused at a sufficiently low temperature, thereby providing substantial cost savings and enabling reduced fuser wear and functioning similarly to conventional toners . A cold-pressing toner composition comprising a colorant and a core of a mixture of a crystalline copolyester-copolydimethylsiloxane and an amorphous resin and a polymer shell covering the core is used. [Selection figure] None

Description

  The present disclosure relates generally to toners and, more particularly, to cold pressure fixing toners comprising a copolyester-copolydimethylsiloxane and amorphous resin core and a polymer shell covering the core.

  Many cold pressure fixing (CPF) toner compositions are known. These toners can function in an electrophotographic apparatus that fixes a toner on paper without selecting a pair of high-pressure rollers and heating them. An example of a cold pressure fixing toner includes an ethylene-vinyl acetate copolymer and a polyamide thermoplastic polymer, each having a specific temperature softening point.

  U.S. Pat. No. 9,405,207 discloses certain types comprising at least one amorphous polyester resin, an optional colorant, an optional wax, and at least one crystalline polyester resin. The toner is shown and the at least one crystalline polyester resin comprises at least one component selected from the group consisting of lactam, lactide, cyclic anhydride, cyclic carbonate, and combinations thereof, lipase, cutinase And an enzyme selected from the group consisting of combinations thereof.

  U.S. Pat. No. 8,273,516 discloses a balloplastic resin comprising a block copolymer comprising at least one soft segment combined with at least one hard segment, and a colorant, wax, coagulant and their A cold pressure fixing toner is shown comprising one or more components selected from the group consisting of combinations.

  U.S. Pat. No. 7,538,157 discloses a composition that can be processed by applying pressure, the composition being a baroplastic material, more specifically at a specific temperature. A composition comprising a first material that is a solid and a second confined material that is a fluid at a particular temperature. Applying sufficient pressure to the composition in particulate form to cause at least a portion of the first material to flow at a temperature at which a portion of the first material remains solid in the absence of pressure, Thereby, at least a portion of the first and second materials are mixed.

For example, at least one crystalline polyester material having a melting point in the range of about 30 ° C. to about 130 ° C. and at least one C ₁₆ -C having a glass transition temperature (Tg) of about −30 ° C. to about 70 ° C. _A cold-fixing toner comprising at least one amorphous organic material, wherein at least one amorphous organic material is a rosin ester, optionally a hydrogenated rosin ester, or optionally a modified rosin ester, This is shown in copending US patent application Ser. No. 15 / 069,453, filed Mar. 14.

US Pat. No. 9,405,207 US Pat. No. 8,273,516 US Pat. No. 7,538,157 US patent application Ser. No. 15 / 069,453

  There is a need for a cold pressure fixing toner and process thereof that minimizes or substantially eliminates the disadvantages presented herein.

  There is also a need for a composition comprising a baroplastic material and a cold pressure fixing toner.

  There is also a need for a cold-fixing toner that can be fused at a sufficiently low temperature, thereby providing substantial cost savings.

  Furthermore, there is another need to provide a cold pressure fixing toner that allows superior and reduced fuser wear compared to some known cold pressure fixing toners.

  In addition, there is a need for cold pressure fixing toner that requires less power to supply fuser components present in electrophotographic copying and printing systems.

  There is also a need for cold pressure fixing toner compositions that have fewer energy requirements for printing and that function similarly to conventional toners.

  Furthermore, there is a need for an environmentally acceptable cold pressure fixing toner that can achieve acceptable permanent fixing of an image to a substrate, and that has acceptable pen offset and excellent charging characteristics. Has been.

  There is also a need for cold pressure fixing toners that include a core produced using solventless emulsification of crystalline polyester.

  Further, a cold pressure fixing toner composition process involving phase inversion emulsification of a crystalline resin-derived core latex is desired.

  These and other needs and advantages can be achieved in embodiments using the processes and compositions disclosed herein.

  A cold pressure fixing toner composition is disclosed comprising a colorant, a core comprising a crystalline copolyester-copolydimethylsiloxane resin and an amorphous resin, and a polymer shell covering the core.

  There is also provided a cold pressure fixing toner comprising a core comprising a colorant, a wax, an optional additive, a mixture of copolyester-copolydimethylsiloxane and an amorphous resin, and a shell comprising a polymer and covering the core. The copolyester-copolydimethylsiloxane disclosed is represented by the following formula / structure:

Wherein R ¹ and R ² are methyl, a is a number from 1 to about 1,000, b is a number from 1 to about 100, m is a number from 2 to about 12, and n is A number from 0 to about 12, p is a number from 5 to about 1,000, a and b represent random segments of copolyester-copolydimethylsiloxane, and the sum of a and b is about 100%.

  And colorants, waxes,

A copolyester-copolydimethylsiloxane crystalline resin represented by: wherein R ¹ and R ² are methyl, a is a number from 1 to about 1,000, and b is from 1 to about 100. M is a number from 6 to about 10, n is a number from 4 to about 10, p is a number from 5 to about 1,000, and a and b are copolyester-copolydimethylsiloxane crystals. Copolyester-copolydimethylsiloxane crystalline resin representing a random segment of a conductive resin and terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxyl) Bisphenol A-fumarate), terpoly- (propoxylated bisphenol A-terephthalate) -Terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly-(ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol) A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellate), poly (propoxylated bisphenol-A-fumarate), copoly (propoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate) , Copoly (ethoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate), copo Li (butoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate), and copoly (propoxylated 1,4-diphenol-fumarate) -copoly (glycerinoxylated-diphenol-fumarate) Cold pressure fixing comprising a core comprising a mixture of an amorphous resin selected from the group consisting of, and a shell surrounding the core, the shell selected from the group comprising styrene acrylate and an amorphous resin A toner composition is disclosed.

Copolyester-copolydimethylsiloxane I. For example, from about 20 wt% to about 80 wt%, from about 10 wt% to about 75 wt%, based on the toner solids content of the core, which is believed to be available from DuPont and is disclosed %, About 25% to about 75%, about 45% to about 50%, or about 50% to about 80% by weight of an example of a copolyester-copolydimethylsiloxane Shown in Formula I.

  Formula I

Wherein R ¹ and R ² are methyl, a, b, m, n and p represent the number of repeating segments, for example, a is a number from 1 to about 1,000 and b is from 1 to about 100. M is a number from about 2 to about 12, n is zero (0), or n is a number from about 2 to about 12, and p is from about 5 to about 10,000. A and b represent random segments of the copolymer, the sum of a and b being about 100%.

  The copolyester-copolydimethylsiloxane selected for the disclosed cold-fixing toner can be represented by the following formula / structure:

Wherein R ¹ and R ² are methyl and a, b, m, n and p represent the number of repeating segments, more specifically, a is from 1 to about 1,000, from about 100 to about 500. Or a number from about 300 to about 700, b is a number from 1 to about 100, from about 50 to about 75, or from about 40 to about 75, and m is from 2 to about 12, or from 6 to about 10. And n is zero (0), or n is a number from about 2 to about 12, or from about 4 to about 10, and p is from 5 to about 1,000, from about 325 to about 725, or A number from about 100 to about 500, a and b representing random segments of the copolymer, the sum of a and b being about 100%.

  In embodiments, as shown herein, the copolyester-copolydimethylsiloxane can be prepared by the reaction of an organic diacid, an organic diol, and a carbinol (hydroxyl) terminated dimethylsiloxane.

  Examples of organic diacids or diesters selected for the preparation of copolyester-copolydimethylsiloxane include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid , Isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid, diesters or anhydrides thereof. The organic diacid can be selected, for example, in an amount of about 45 to about 55 mole percent of the resin.

  Examples of organic diols selected for the preparation of the disclosed copolyester-copolydimethylsiloxanes include aliphatic diols having from about 2 to about 36 carbon atoms, particularly alkyl diols such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,12-dodecanediol and the like. The aliphatic diol is selected, for example, in an amount of about 45 to about 55 mole percent of the resin.

  An example of a carbinol (hydroxyl) terminated polydimethylsiloxane selected for the preparation of the disclosed copolyester-copolydimethylsiloxane is bis (3-hydroxypropyl) available from Gelest as DMS-15 to DMS-23. -Polydimethylsiloxane, bis (2-hydroxyethyl) -polydimethylsiloxane, bis (4-hydroxybutyl) -polydimethylsiloxane, and the weight average molecular weight of the carbinol (hydroxyl) terminated polydimethylsiloxane diol was determined by gel permeation chromatography. As measured by graphy (GPC analysis), for example, from about 300 to 30,000 g / mol, for example showing a viscosity from about 30 centistokes to about 300 centistokes.

The copolyester-copolydimethylsiloxanes selected for the disclosed pressure fixing toners have a number average molecular weight (M) of, for example, from about 2,000 daltons to about 50,000 daltons, or from about 4,000 daltons to about 10,000 daltons. _n ), having a weight average molecular weight (M _w ) of about 5,000 daltons to about 100,000 daltons, or about 10,000 daltons to about 50,000 daltons, the molecular weight of which is determined by gel permeation chromatography Can be measured.

  The specific crystalline copolyester-copolydimethylsiloxane included in the cold-fixed core exemplified herein is copoly (hexylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane), copoly (butylene decadeca). Noate) -copoly- (3-propyl-dimethylsiloxane), copoly- (ethylene sebacate) -copoly- (3-propyl-dimethylsiloxane), copoly- (butylene sebacate) -copoly- (3-propyl-dimethyl) Siloxane), copoly- (butylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane), resin A copoly- (ethylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane), resin B copoly -(Nonylenedodecanoate) -copoly- (3-propyl-dimethylsilane) Hexane), and optionally, a mixture thereof and the resin A and the resin B having the properties shown in Table 1 as disclosed herein.

Compatible Amorphous Resins Cores of the disclosed cold-fixed toner include, for example, from about 25% to about 80%, from about 25% to about 50%, from about 20% to about 50% by weight of the toner Or terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-), or in an amount of about 50% to about 60% by weight. Fumarate), terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dode) Decenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate), poly (propoxylated bisphenol A-cofumarate), copoly (propoxylated bisphenol-fumarate) -copoly (Trimethylolpropoxylated-bisphenol-fumarate), copoly (ethoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate), copoly (butoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated) -Bisphenol-fumarate), copoly (propoxylated 1,4-diphenol-fumarate) -copoly (glycerinoxylated-diphe Lumpur - fumarate), and mixtures thereof, may include many suitable amorphous resins.

Amorphous polyester resins are measured by GPC using polystyrene standards such as, for example, about 5,000 to about 100,000, about 10,000 to about 75,000, or about 5,000 to about 50,000. Can have a number average molecular weight (M _n ). The weight average molecular weight (M _w ) of the amorphous polyester resin is, for example, from about 2,000 to about 100,000, from about 15,000 to about 85,000, or from about 5, as measured by GPC using polystyrene standards. 000 to about 80,000. The molecular weight distribution ( _Mw / _Mn ) or polydispersity of the amorphous polyester resin is, for example, from about 2 to about 8, from about 2 to about 6, or from about 3 to about 5.

Optional Wax For the toners shown herein, a number of suitable optional waxes are selected, including the wax in the disclosed core, at least one shell, and both the core and at least one shell. Can do.

  Examples of optional waxes selected for the disclosed toners include polyolefins such as polypropylene, polyethylene and the like (such as those available from Allied Chemical and Baker Petrolite Corporation), Michaelman Inc. And wax emulsions available from Daniels Products Company, Eastman Chemical Products, Inc. EPOLENE N-15 ™, commercially available from Viscol 550-P ™, a low weight average molecular weight polypropylene available from Sanyo Chemical Industries, Ltd., and similar materials. Examples of functionalized waxes that can be selected for the disclosed toners include amines, amides (eg, AQUA SUPERSLIP 6550 ™ and SUPERSLIP 6530 ™, both available from Micro Powder Inc.), fluorine Wax (eg, POLYFLUO 190 ™, POLYFLUO 200 ™, POLYFLUO 523XF ™, AQUA POLYFLUO 411 ™, AQUA POLYSILK 19 ™, and POL14 ™, all available from Micro Powder Inc. )), Mixed fluorinated amide waxes (eg, MICROSPERSION 19 ™ available from Micro Powder Inc), imides, Steal, quaternary amine, carboxylic acid or acrylic polymer emulsions (eg, JONCRYL 74 ™, 89 ™, 130 ™, 537 ™ and 538 ™ all available from SC Johnson Wax), Chlorinated polypropylene and chlorinated polyethylene (available from Allied Chemical, Petrolite Corporation and SC Johnson Wax).

  The wax is, for example, a wax having a particle size of about 100 nanometers to about 500 nanometers or about 100 nanometers to about 300 nanometers, water, an anionic surfactant or polymer stabilizer, and optionally non- It may be in the form of a dispersion containing an ionic surfactant. In embodiments, the wax is polyethylene wax particles such as POLYWAX® 655 or POLYWAX® 725, POLYWAX® 850, POLYWAX® 500 (POLYWAX commercially available from Baker Petrolite), And fractionated / distilled wax that is a distillation portion of the commercially available POLYWAX® 655, referred to as, for example, X1214, X1240, X1242, X1244, and the like.

  In embodiments, the wax is, for example, a wax having a particle size of about 100 nanometers to about 500 nanometers or about 100 nanometers to about 300 nanometers, water, an anionic surfactant or polymer stabilizer, and any It is in the form of a dispersion containing a nonionic surfactant selectively. In embodiments, the wax selected for the disclosed toner is POLYWAX® 655 or POLYWAX® 725, POLYWAX® 850, POLYWAX® 500 (POLYWAX® wax). Are commercially available from Baker Petrolite) and fractionated / distilled waxes (eg, US Pat. No. 7,553,596) which is a distillation portion of, for example, commercially available POLYWAX® 655. And the specification of US Pat. No. 7,749,670), which are incorporated herein by reference in their entirety. Examples of other toner waxes include FT-100 wax available from Shell (SMDA) and FNP0092 available from Nippon Seiwa Co., Ltd. Surfactants used to disperse the wax are, for example, NEOGEN RK (registered trademark) commercially available from Daiichi Kogyo Seiyaku Co., Ltd., TAYCAPOWER (registered trademark) BN 2060 commercially available from Teika Co., Ltd. Or E. I. It may also be an anionic surfactant such as DOWFAX® available from DuPont.

  Also, a wax having a specific viscosity / temperature standard can be selected, with the upper limit of viscosity being for example about 10,000 cps and the upper limit of temperature being for example about 100 ° C. These waxes can have a particle size in the range of, for example, about 100 nanometers to about 500 nanometers, or about 200 nanometers to about 375 nanometers.

  The amount of toner wax is, for example, from about 0.1% to about 20%, from about 0.5% to about 15%, from about 1% to about 12%, based on the solids content of the toner, About 1% to about 10%, about 4% to about 9%, about 1% to about 5%, about 1% to about 4%, or about 1 to about 3% by weight obtain.

Optional Colorants Examples of toner colorants present in the core of the disclosed cold-fixing toner include pigments, dyes, pigment-dye mixtures, pigment mixtures, dye mixtures, and the like. In embodiments, the colorant includes carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, and mixtures thereof.

  The toner colorant can be selected from, for example, cyan, magenta, yellow or black pigment dispersions, each color being included in an anionic surfactant, or optionally in a nonionic surfactant. For example, pigment particles having a volume average particle size of from about 50 nanometers to about 300 nanometers, and from about 125 nanometers to about 200 nanometers. The surfactant used to disperse each colorant may be any number of known ingredients, such as an anionic surfactant such as NEOGEN RK ™. Known optimizer stirrers can be used to provide the colorant dispersion, but media mills or other known processes may be utilized.

  The amount of toner colorant varies, for example from about 1% to about 50% by weight of total solids, from about 2% to about 40%, from about 2% to about 30%, from 1% to It can be about 25%, 1% to about 18%, 1% to about 12%, 1% to about 6%, or about 3 to about 10% by weight. When selecting a magnetite pigment for the toner, the amount is based on total solids, such as from about 40 wt% to about 80 wt%, or from about 50 wt% to about 75 wt% solids up to about 80 wt% It can be.

  Specific toner colorants that may be selected for the disclosed toners include PALIOGEN VIOLET 5100 ™ and 5890 ™ (BASF), NORMANDY MAGENTA RD-2400 ™ (Paul Ulrich), PERMANENT VIOLET VT2645 (trademark). ) (Paul Ulrich), HELIOGEN GREEN L8730 (trademark) (BASF), ARGYLE GREEN XP-111-S (trademark) (Paul Ulrich), BRILLIANT GREEN TONER GR0991 (trademark) (Paul UlrLET LET3) BASF), TOLUIDINE RED ™ (Aldrich), Scarlet for THERMOPLAST NSD RED (TM) (Aldrich), LITHORU RUBINE TONER (TM) (Paul Ulrich), LITHOL SCARLET 4440 (TM), NBD 3700 (TM) (BASF), BON RED C (TM) IOLRO RED RD-8192 (TM) (Paul Ulrich), ORACET PINK RF (TM) (Ciba Geigy), PALIOGEN RED 3340 (TM) and 3871K (TM) (BASF), LITHOL FAST SCARLET L4300 (TM), (BASF) (EL) BLUE D6840 (trademark), D7080 (trademark), K7090 (trademark), K6 10 (TM) and L7020 (TM) (BASF), SUDAN BLUE OS (TM) (BASF), NEOPEN BLUE FF4012 (TM) (BASF), PV FAST BLUE B2G01 (TM) (American Hoechst), IRGALITE BLUE BCA (TM) ) (Ciba Geigy), PALIOGEN BLUE 6470 (TM) (BASF), SUDAN II (TM), III (TM) and IV (TM) (Matheson, Coleman, Bell), SUDAN ORANGE (TM) (Aldrich), SUDARANANG 220 (trademark) (BASF), PALIOGEN ORANGE 3040 (trademark) (BASF), ORTHO ORANGE OR 2673 ( (Trademark) (Paul Ulrich), PALIOGEN YELLOW 152 (trademark) and 1560 (trademark) (BASF), LITHOL FAST YELLOW 0991K (trademark) (BASF), PALIOTOEL YELLOW 1840 (trademark) (BASF), NOVAPERM EL Hoechst), PERMANERIT YELLOW YE 0305 (trademark) (Paul Ulrich), LUMOGEN YELLOW D0790 (trademark) (BASF), SUCO-GELB 1250 (trademark) (BASF), SUCO-YELLOW D1355 WST (BAS), BAST D1165 ™, D1355 ™ and D1351 ™ (BASF), H STAPER PIN E (TM) (Hoechst), FANAL PINK D4830 (TM) (BASF), CINQUASIA MAGENTA (TM) (DuPont), PALIOGEN BLACK L9984 (TM) (BASF), PIGMENT BLACK K801S (TM) Carbon blacks such as REGAL® 330 (Cabot), CARBON BLACK 5250 ™ and 5750 ™ (Columbian Chemicals), mixtures thereof, and the like.

  Examples of colorants in the aqueous dispersion include those commercially available from Sun Chemical, such as SUNPERSE BHD 6011 ™ (Blue 15 type), SUNPERSE BHD 9312 ™ (Pigment Blue 15), SUNPERSE BHD 6000 ( Trademark) (Pigment Blue 15: 3 74160), SUNPERSE GHD 9600 (Trade Mark) and GHD 6004 (Trade Mark Green 7 74260), SUNPERSE QHD 6040 (Trade Mark) (Pigment Red 122), SUNPERSE RHD 9668 (Trade Mark) (Pigment) Red 185), SUNPERSE RHD 9365 ™ and 9504 ™ (Pigment Red 57), SUNPERSE YH 6005 (TM) (Pigment Yellow 83), FLEXIVERSE YFD 4249 (TM) (Pigment Yellow 17), SUNSPERSE YHD 6020 (TM) and 6045 (TM) (Pigment Yellow 74), SUNSPERSE YHD 600 (TM) and 9604 (TM) (Pigment Yellow 14), FLEXIVERSE LFD 4343 (TM) and LFD 9736 (TM) (Pigment Black 7), mixtures thereof and the like. Aqueous colorant dispersions that can be selected for the toner compositions disclosed herein include those commercially available from Clariant, such as HOSTAFINE Yellow GR ™, HOSTAFINE Black T ™, and Black TS. ™, HOSTAFINE Blue B2G ™, HOSTAFINE Rubine F6B ™, and dry magenta pigments such as Toner Magenta 6BVP2213 and Toner Magenta EO2, which can disperse the pigment in water and / or surfactant. .

  Examples of toner pigments selected and available in concentrated form containing wet cake or water can be easily dispersed in water using a homogenizer or simply by stirring, ball milling, grinding or media milling. In other examples, the pigment is only available in dry form, and the dispersion in water uses, for example, an M-110 microfluidizer or optimizer, and the pigment dispersion is passed through the microfluidizer chamber for about 1 ~ Fluidized by passing about 10 times, or sonication such as using a Branson 700 sonicator, or optional dispersing agent such as ionic or non-ionic surfactant in homogenizer, ball mill, grinding or media mill Caused by selective addition.

  Examples of specific colorant magnetites include Mobay's magnetite MO8029 ™, MO8960 ™, Colombian magnetite MAPICO BLACKS ™ and surface treated magnetite, Pfizer's magnetite CB4799 ™, CB5300 ™, CB5600. ™, MCX6369 ™, Bayer's magnetite BAYFERROX 8600 ™, 8610 ™, Northern Pigments' magnetite NP-604 ™, NP-608 ™, Magnox's magnetite TMB-100 ™ Or TMB-104 ™, or mixtures thereof. Colored magnetites such as MAPICO BLACK ™ and a mixture of cyan components can also be selected as colorants.

  Furthermore, specific examples of pigments present in the toner core include Paul Ulrich & Company, Inc. Phthalocyanine HELIOGEN BLUE L6900 (TM), D6840 (TM), D7080 (TM), D7020 (TM), PYLAM OIL BLUE (TM), PYLAM OIL YELLOW (TM), PIGMENT BLUE 1 (TM), DOMINION COLOR CORPORATION, Ltd. (PIGMENT VIOLET 1 ™, PIGMENT RED 48 ™, LEMON CHROME YELLOW DCC 1026 ™, available from E.C. D. TOLUIDINE RED (TM) and BON RED C (TM), NOVAPERM YELLOW FGL (TM) from Hoechst, HOSTAPERM PINK E (TM), E.I. I. CINQUASIA MAGENTA ™ available from DuPont de Nemours & Company and the like. Examples of magenta include, for example, 2,9-dimethyl substituted quinacridone, and anthraquinone dyes identified as CI 60710, CI Dispersed Red 15 by color index, diazo dyes identified as CI 26050, CI Solvent Red 19 by color index Or similar, or mixtures thereof. Specific examples of cyan are identified as CI74160 in the color index, copper tetra (octadecylsulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed as CI pigment blue, and DI69810 in the color index, Special Blue X-2137. Anthracrene Blue, and the like, or mixtures thereof. Specific examples of yellow that can be selected include 3,3-dichlorobenzideneacetoacetanilide, which is diarylide yellow, a monoazo pigment identified as CI 12700, CI Solvent Yellow 16 by color index, and Foron Yellow SE / Nitrophenylamine sulfonamide identified as GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,4-dimethoxyacetoacetanilide, and Permanent Yellow FGL . The pigment dispersion includes pigment particles dispersed in an aqueous medium using an anionic dispersant / surfactant or a nonionic dispersant / surfactant, and the amount of dispersant / surfactant is, for example, about 0.5 to about 10% by weight.

Shell The disclosed core comprising the components exemplified herein comprises from about 1 to about 5 shells of amorphous resin, styrene acrylate resin or mixtures thereof, more specifically from about 1 to about 3 Or more specifically about 1 to about 2 shells. Each shell can have a known suitable effective thickness, for example, from about 0.2 microns to about 2 microns, or from about 0.5 microns to about 1 micron. Examples of shells include styrene acrylate, copolymers with styrene, and acrylates selected from the group consisting of, for example, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate, and the like. All of these are available from Monsanto Chemicals. Also, the shells are terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate), and terpoly- (propoxylated). Bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated) Bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate), etc. It may include compatible core polymers disclosed in Saisho. The shell is formed, for example, covering about 80% to about 100% of the core, about 90% to about 100% of the core, 85% to about 99% of the core, or about 95% to about 99% of the core. .

  Examples of specific styrene acrylates selected for the disclosed shell include polystyrene-acrylate, polystyrene-methacrylate, polystyrene-butadiene, polyacetate, polyacrylate, polymethacrylate polystyrene-2-ethylhexyl acrylate, polystyrene-2- Ethyl hexyl methacrylate, mixtures thereof, and the like.

  The shell resin can be applied to the aggregated toner particles or coalesced toner particles by various known methods. Emulsions having a shell component can be combined with agglomerated toner particles such that a shell is formed on the agglomerated particles. Formation of a shell or at least one shell on the agglomerated particles can occur while heating to a temperature of about 30 ° C to about 80 ° C, or about 35 ° C to about 70 ° C. Shell formation may occur for about 5 minutes to about 10 hours, or for about 10 minutes to about 5 hours. The shell can be present in an amount from about 1% to about 80% by weight of the toner component, from about 10% to about 40% by weight of the toner, or from about 20% to about 35% by weight of the toner.

Additives The cold pressure fixing toners exemplified herein include, for example, the antioxidant IRGANOX® 1010 available from Ciba, NAUGARD® 76, NAUGARD® all available from Addivant. ) 445, NAUGARD (registered trademark) 512, NAUGARD (registered trademark) 524, Mayzo Inc. Many known, such as MAYZO® BNX® 1425, a calcium salt of phosphonic acid available from, and MAYZO® BNX® 358, nonylphenol disulfide, and ETHANOX® 323A For example, from about 0.01% to about 25% by weight of CPF toner solids, from about 0.1% to about 25%, or from about 1% to about It can be present in an amount of 20% by weight.

  Further, the CPF toner disclosed herein includes plasticizers such as Uniplex 250 commercially available from Unitex, dioctyl phthalate, diundecyl phthalate and phthalic acid commercially available under the trade name SANTICIZER® from Ferro. Phthalate plasticizers such as alkylbenzyl (SANTICIZER® 278), triphenyl phosphate commercially available from Ferro, KP-140, a tributoxyethyl phosphate commercially available from Great Lakes Chemical Corporation, Morflex Chemical Company Inc. MORFLEX® 150, a dicyclohexyl phthalate commercially available from Sigma Aldrich Co. It may further contain trioctyl trimellitic acid available from and the like. The plasticizer is present, for example, in an amount of about 0.01% to about 30%, about 0.1% to about 25%, or about 1% to about 20% by weight of CPF toner solids. May be.

Preparation of Toner The cold-fixing toner compositions exemplified herein are disclosed in, for example, US Pat. Nos. 5,593,807, 5,290,654, and 5,308,734. No. 5,370,963, No. 6,120,967, No. 7,029,817, No. 7,736,832, No. 8,466,254 No. 9,428,622 and 9,410,037, and can be prepared by emulsion aggregation / union methods as described in many patents.

  Thus, the disclosed cold-fix toners aggregate a mixture of any colorant, any wax, and any toner additive with an emulsion comprising the disclosed copolyester-copolydimethylsiloxane, and a compatible polymer core. Can then be prepared by an emulsification / aggregation / union process, such as a process that includes the step of coalescing the agglomerated mixture. The resin mixture emulsion contains a stabilizer and optionally a surfactant after dissolving the disclosed copolyester-copolydimethylsiloxane, a compatible amorphous polymer, and optional additives in a suitable solvent. It can be prepared by a known phase inversion process by adding water such as deionized water.

  In some embodiments, the toner composition agglomerates a mixture of optional colorant, optional wax and optional toner additive with an emulsion comprising a copolyester-copolydimethylsiloxane and an amorphous resin, and then aggregates Can be prepared by a number of known emulsification / aggregation / union processes, such as processes involving coalescence of the resulting mixture. The emulsion is prepared by dissolving the copolyester-copolydimethylsiloxane and amorphous resin in a suitable solvent and then adding water such as deionized water containing a stabilizer and optionally a surfactant. Can be prepared by known phase inversion processes. See generally US Pat. Nos. 9,428,622 and 9,410,037. Both of these are incorporated herein in their entirety.

  Suitable dissolving solvents include alcohols, ketones, esters, ethers, chlorinated solvents, nitrogen containing solvents, and mixtures thereof. Specific examples of suitable solvents include acetone, methyl acetate, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, ethyl acetate, N, N dimethylformamide, dioctyl phthalate, toluene, xylene, benzene, dimethyl sulfoxide, mixtures thereof and the like. It is done. The amorphous polyester and copolyester-copolydimethylsiloxane core resin mixture can be dissolved in the solvent at an elevated temperature of about 40 ° C to about 80 ° C, such as about 50 ° C to about 70 ° C, or about 60 ° C to about 65 ° C. The desired temperature is lower than the glass transition temperature of the wax (if present) or resin mixture. Thus, the core resin mixture can be melted at a high temperature but below the boiling point of the solvent, such as about 2 ° C. to about 15 ° C., or about 5 ° C. to about 10 ° C. below the boiling point of the solvent.

  Examples of any suitable stabilizer selected for the toner process exemplified herein include aqueous ammonium hydroxide, water soluble alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide). , Beryllium hydroxide, magnesium hydroxide, calcium hydroxide or barium hydroxide), ammonium hydroxide, alkali metal carbonates and bicarbonates (such as sodium bicarbonate, lithium bicarbonate, potassium bicarbonate), lithium carbonate, potassium carbonate Sodium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, barium carbonate or cesium carbonate, or mixtures thereof. Stabilizers can be present, for example, in amounts of about 0.1% to about 5%, about 0.5% to about 3% by weight of solids such as colorants, waxes and resin mixtures. When a salt is added as a stabilizer, it may be desirable in embodiments that no incompatible metal salt is present.

  If desired, as disclosed herein, a surfactant can be added to the disclosed aqueous emulsion media to provide further stabilization of the core resin mixture. Suitable surfactants include anionic, cationic and nonionic surfactants.

  Examples of anionic surfactants include sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate, sodium dodecyl naphthalene sulfate, dialkylbenzene alkyl, sulfate and sulfonate, abitic acid and NEOGEN® brand anions. A surfactant is included. Specific examples of suitable anionic surfactants are NEOGEN (registered trademark) RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Japan) or TAYCAPOWER (registered trademark) available from Teika Co., Ltd. (Japan). BN2060 (mainly composed of branched sodium dodecylbenzenesulfonate) can be selected.

Examples of cationic surfactants include dialkyl benzene alkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetylpyridinium _{bromide, C 12, C 15, C} 17 Trimethylammonium bromide, quaternized polyoxyethylalkylamine halide salt, dodecylbenzyltriethylammonium chloride, MIRAPOL® and ALKAQUAT® available from Alcaril Chemical Company, SANISOL® available from Kao Chemicals SANISOL® benzyldimethyl such as B-50 Benzalkonium chloride, and a similar thing.

  Examples of nonionic surfactants include IGEPAL (R) CA-210, IGEPAL (R) CA-520, IGEPAL (R) CA-720, IGEPAL (R) CO-890, IGEPAL (R) Trademarks: CG-720, IGEPAL (R) CO-290, ANTAROX (R) 890, and ANTAROX (R) 897 (mainly composed of alkylphenol ethoxylates and available from Rhone-Poulenc Inc.) Poulenc Inc. Polyvinyl alcohol, polyacrylic acid, metalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether available from , Polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly (ethyleneoxy) ethanol.

  Further related to the emulsification / agglomeration / union process following agglomeration, the formed agglomerates can be coalesced as shown herein. Coalescence can be achieved by heating the resulting agglomerated mixture to a temperature about 5 ° C. to about 30 ° C. above the glass transition temperature (Tg) of the copolyester-copolydimethylsiloxane. In general, the agglomerated mixture may be heated to a temperature of about 50 ° C. to about 90 ° C., and the agglomerated mixture may be stirred at about 200 revolutions / minute to about 750 revolutions / minute to help coalesce the particles, The coalescence may be achieved, for example, over a period of about 3 hours to about 9 hours.

  Optionally, the particle size of the toner particles can be controlled to the desired size during coalescence by adjusting the pH of the resulting mixture. In general, the pH of the formed mixture can be adjusted to about 5 to about 8 by adding a base, such as sodium hydroxide, to control the particle size measured with a Coulter counter.

  After coalescence, the mixture may be cooled to room temperature of about 20 ° C. to about 25 ° C., and the resulting toner particles may be washed with water and then dried. Drying may be accomplished by any suitable method, including lyophilization, and is typically accomplished at a temperature of about −80 ° C. for about 72 hours.

After aggregation and coalescence, the toner particles in embodiments are about 1 micron to about 15 microns, about 4 microns to about 15 microns, or about 6 microns to about 11 microns, for example about 7 microns as measured with a Coulter Counter. Having an average particle size. The volumetric size distribution (GSD _V ) of the toner particles may be from about 1.20 to about 1.35 as measured with a Coulter counter, and in embodiments may be less than about 1.25. .

  Further, in embodiments of the present disclosure, a colorant, and optionally a core of wax and other toner components, stabilizers, surfactants, and the disclosed copolyester-copolydimethylsiloxane mixture, and a compatible amorphous A pre-toner mixture can be prepared by combining polymers into one or more emulsions. The pH of the pre-toner mixture can be adjusted to about 2.5 to about 4 by adding an acid such as acetic acid, nitric acid or the like. The pre-toner mixture can optionally be homogenized, for example, using a TKA ULTRA TURRAX T50 probe homogenizer, for example, by mixing the mixture at about 600 to about 4000 revolutions / minute.

  Following preparation of the pre-toner mixture, an agglomerate mixture can be formed by adding a flocculant (coagulant) to the pre-toner mixture. The flocculant is generally composed of an aqueous solution of a divalent cation or a multivalent cation material. Flocculants include, for example, polyaluminum chloride (PAC) or the corresponding bromide, polyaluminum halides such as fluoride or iodide, polyaluminum silicates such as polyaluminum sulfosilicate (PASS), and aluminum chloride, nitrous acid Aluminum, Aluminum sulfate, Calcium sulfate, Calcium acetate, Calcium chloride, Calcium nitrite, Calcium oxide, Calcium sulfate, Magnesium acetate, Magnesium nitrate, Magnesium sulfate, Zinc acetate, Zinc nitrate, Zinc sulfate, Zinc chloride, Zinc bromide, It may be a water-soluble metal salt including magnesium bromide, copper chloride, copper sulfate and combinations thereof. In embodiments, the flocculant may be added to the pre-toner mixture at a temperature below the glass transition temperature (Tg) of the emulsion resin. The flocculant can be added, for example, in an amount of about 0.05 to about 3 pph (parts per hundred), or about 1 to about 10 pph based on the weight of the toner. The flocculant can be added to the pre-toner mixture, for example, over a period of about 10 to about 60 minutes.

  To control particle agglomeration and coalescence, for example, at least about 5 minutes to about 240 minutes, about 5 minutes to about 200 minutes, about 10 minutes to about 100 minutes, about 15 minutes to about 50, if desired. The flocculant can be metered into the selected resin-containing mixture over a period of about 5 minutes or about 5 minutes to about 30 minutes. The addition of the flocculant is performed under stirring conditions of the core-containing mixture from about 50 rpm to about 1,000 rpm, or from about 100 rpm to about 500 rpm, and below the glass transition temperature of the core resin mixture, such as a temperature of about 10 ° C. to about 40 ° C. It can also be performed while maintaining.

  The formed particles can be agglomerated until a predetermined desired particle size is obtained, and the particle size is monitored during the growth process until the desired or predetermined particle size is achieved. During the growth process, a composition sample can be removed and analyzed using, for example, a Coulter counter to determine and measure the average particle size. In this way, the temperature is slowly increased, for example from about 35 ° C. to about 100 ° C., or from about 35 ° C. to about 45 ° C., and the resulting mixture is allowed to reach, for example, about 0.5 hours to about 6 hours, or Agglomeration can proceed by maintaining agitation for a period of about 1 hour to about 5 hours to provide agglomerated particles.

  Once the desired final size of the agglomerated toner particles is achieved, the pH of the mixture can be adjusted to a value of about 6 to about 10, or about 6.2 to about 7, with a base. Adjustment of the pH can be used to freeze, i.e. to stop toner particle growth. The base used to stop toner growth may include any suitable base such as alkali metal hydroxides including sodium and potassium hydroxide, ammonium hydroxide, combinations thereof and the like. it can. In certain embodiments, ethylenediaminetetraacetic acid (EDTA) can be added to help adjust the desired pH. In certain embodiments, the base can be added in an amount of about 2 to about 25% by weight of the mixture, more specifically about 4 to about 10% by weight of the mixture.

  More specifically, in embodiments, the cold fix toner of the present disclosure produces a latex emulsion comprising a core of (i) a mixture of a copolyester-copolydimethylsiloxane, an amorphous polymer, and optional additives. Or supplying and producing or supplying a colorant dispersion containing a colorant, water and an ionic or nonionic surfactant; (ii) optionally making the latex emulsion a colorant dispersion (Iii) coagulating the resulting blend with a polymetal ion coagulant, metal ion coagulant, polymetal halide coagulant, metal halide coagulant, or mixtures thereof. (Iv) adding the resulting mixture to a copolyester-copolydimethylsiloxane or non-embodiment By agglomerating by heating to a temperature less than or approximately equal to the glass transition temperature (Tg) of the porous polyester resin to form a core, and (v) adding a shell polymer of styrene acrylate or amorphous resin And (vi) introducing sodium hydroxide solution to raise the pH of the resulting mixture to about 4, and then adding a sequestering agent to control any agglomeration in a controlled manner from the agglomerated particles. (Vii) the resulting mixture of (vi) is approximately equal to the Tg of the copolyester-copolydimethylsiloxane or amorphous polyester resin mixture at a pH of about 7 to about 9; Heating to an equal or above temperature; and (viii) melting of the resin, wax, if present, and colorant or Holding the heating until one is started, and (ix) changing the pH of the mixture of (viii) by adding acid to reach a pH of about 6 to about 7.5, thereby melting Or a toner that promotes coalescence and includes a core of amorphous polyester, copolyester-copolydimethylsiloxane, a wax, and a colorant, if present, in a styrene acrylic shell or in an amorphous resin shell It can be prepared by emulsification / aggregation / combination by generating particles and (x) optionally isolating the toner.

  After agglomeration to the desired particle size, the particles can be coalesced to the desired final particle size and shape, such as from about 55 ° C to about 100 ° C, from about 75 ° C to about 90 ° C, about It is achieved by heating to any desired or effective temperature, such as 65 ° C to about 75 ° C, or about 70 ° C. The coalescence can proceed and be performed over any desired or effective period, such as from about 0.1 hours to about 10 hours, from about 0.5 hours to about 8 hours, or about 4 hours.

After coalescence, the mixture can be cooled to room temperature, typically about 20 ° C to about 25 ° C. Cooling can be fast or slow as needed. A suitable cooling method may include introducing cold water into a jacket around the reactor. After cooling, optionally, the toner particles can be washed with water and then dried. Drying is, for example, a low number of geometric standards of about 1.15 to about 1.40, about 1.18 to about 1.25, about 1.20 to about 1.35, or 1.25 to about 1.35. including lyophilized resulting toner particles having a relatively narrow particle size distribution deviation (GSD _n) ratio, it can be accomplished by any suitable drying method.

Cold-fixed toner particles prepared according to the present disclosure are disclosed herein in embodiments from about 1 to about 25, from about 1 to about 15, from about 1 to about 10, or from about 2 to about 5 microns. Volume average diameter (also referred to as “volume average particle size” or “D50 _v ”). D50 _v , GSD _v and GSD _n can be measured using a measuring instrument such as a Beckman Coulter Multisizer 3 operating according to the manufacturer's instructions. Typical sampling can be performed as follows. About 1 g of a small amount of toner sample can be selected and filtered through a 25 micrometer screen, then placed in an isotonic solution to a concentration of about 10%, and then the sample can be subjected to a Beckman Coulter Multisizer 3.

  The disclosed toner particles can have a shape factor of SF1 * a of about 105 to about 170, or about 110 to about 160. Using a scanning electron microscope (SEM), toner form factor analysis by SEM and image analysis (IA) can be obtained. The average particle shape is quantified using the following shape factor (SF1 * a = 100d2 / (4A)), where A is the area of the particle and d is its principal axis. A perfectly circular or spherical particle has a shape factor of exactly 100. The shape factor SF1 * increases as the shape becomes more irregular or elongated and the surface area increases.

Toner Additives A variety of suitable surface additives can be selected for the disclosed cold pressure fixing toner compositions. An example of an additive is surface-treated fumed silica, such as TS-530 (registered trademark) available from Cabosil Corporation, which has a particle size of 8 nanometers and is surface-treated hexamethyldisilazane. (Trademark), DTMS (available from DeGussa / Nippon Aerosil Co., Ltd.), NAX50 (silica) silica coated with HMDS, obtained from Cabot Corporation, and a fumed silica silicon dioxide core L90 coated with DTMS ( (Registered trademark) Silica, obtained from Wacker Chemie, is available from metal oxides such as H2050EP®, TiO _{2 and the} like coated with amino-functionalized organopolysiloxane, such as Teika Co., Ltd. Has a particle size of meters MT-3103 (registered trademark) surface-treated with decylsilane, available from Teika Co., Ltd., SMT5103 (registered trademark) coated with a DTMS crystalline titanium dioxide core MT500B, available from Degussa Chemicals, P-25 (R) without surface treatment, metal oxides such as aluminum oxide, stearates as lubricants, or long chain alcohols such as UNXLIN 700 (R), and the like. In general, silica is applied to the toner surface for toner flow, triboelectric enhancement, mixing control, improved development and transfer stability, and higher toner blocking temperatures. TiO ₂ is added for relative humidity (RH) stability, friction control, improved development and transfer stability.

  Silicon oxide and titanium oxide surface additives are more specifically measured, for example, by transmission electron microscopy (TEM) or calculated from gas absorption, or BET surface area measurements (assuming spherical particles). The total coverage of the toner should have a primary particle size greater than about 30 nanometers or at least 40 nanometers, for example, ranging from about 140 to about 200% theoretical surface area range (SAC) Where the theoretical SAC assumes that all toner particles are spherical and have a diameter equal to the volume median diameter of the toner measured by the standard Coulter Counter method, and It is calculated on the assumption that the additive particles are distributed as primary particles on the toner surface in a closely packed hexagonal structure. Another metric for additive amount and size is the sum of SAC times size (surface area coverage x additive primary particle size in nanometers) for each of the silica and titania particles. The ratio of silica to titania particles is generally from about 50% silica / 50% titania to about 85% silica / 15% titania (weight percent basis).

  For example, by selecting calcium stearate, zinc stearate or mixtures thereof in an amount of about 0.1 wt% to about 4 wt% as a toner additive to increase the number of contacts between the toner and carrier particles, It can primarily provide superior toner lubrication properties, improved developer conductivity and triboelectric charge enhancement, higher toner charge and charge stability. Examples of toner surface additive stearates selected include SYNPRO®, calcium stearate 392A and SYNPRO®, calcium stearate NF Vegtable, or zinc stearate-L.

In the disclosed cold-fixing toner, it may be desirable to cause the toner material to flow near room temperature under the selected pressure of the cold-fixing system, which causes the toner to flow over the substrate surface and the substrate fines. It can flow into the pores or fibers and allow toner particles to flow into each other, providing a smooth continuous toner layer that effectively adheres to a substrate such as paper. The disclosed cold pressure fixing toner flow can be measured using a CFT-500D Flooster ™ available from Shimadzu Corporation. Also, it may be desirable for the pressure applied to the disclosed cold pressure toner to be relatively low, such as about 100 kgf / cm ² (kilogram / square centimeter pressure units; about 1,423 psi). However, in embodiments, the pressure can be raised to, for example, about 400 kgf / cm ² by heat applied to preheat the substrate, such as toner or paper, before the toner enters the cold pressure fusing system.

Developer Composition The present disclosure also includes a developer composition comprising the toner and carrier particles exemplified herein.

  Examples of carrier particles suitable for mixing with the disclosed cold fix toner compositions include toner particles such as granular zircon, granular silicon, glass, steel, nickel, ferrite, iron ferrite, silicon dioxide and the like. Particles capable of triboelectrically obtaining a charge of the opposite polarity are included. The selected carrier particles can be used with or without a coating, which is generally a polyvinylidene fluoride resin, a terpolymer of styrene, a silane such as methyl methacrylate, triethoxysilane, tetrafluoro It is composed of fluoropolymers such as ethylene, other known coatings, and the like.

  In applications where the described CPF toner is used with an image development apparatus that uses roll fusing, the carrier core is at least partially coated with a polymethylmethacrylate (PMMA) polymer commercially available from Soken Chemicals, about 300 May have a weight average molecular weight of from about 50,000 to about 350,000. PMMA is generally an electropositive polymer that imparts a negative charge on the disclosed cold pressure fixing toner. The carrier coating can be, for example, from about 0.1% to about 5%, or from about 0.5% to about 2% by weight of the carrier. PMMA is optionally copolymerized with various known commons such as monoalkyl or dialkylamines such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, tert-butylaminoethyl methacrylate and mixtures thereof. May be.

  The carrier particles can be any suitable suitable for the disclosed cold-fixed toner particles, such as, for example, mixing about 1 to about 5 parts by weight of toner particles with about 10 to about 300 parts by weight of toner particles. Can be mixed in combination.

  The present disclosure also provides a toner by applying the disclosed cold pressure fixing toner to an imaged photoconductor, transferring the resulting developed image to a suitable substrate, such as paper, and exposing the toner to pressure. A method of developing a latent electrophotographic image comprising fusing a substrate to a substrate is provided.

  Hereinafter, specific embodiments will be described in detail. These examples are illustrative and are not limited to the materials, conditions, or process parameters described herein. Unless otherwise noted, all parts are percentages of solids and particle size was measured with a Multisizer 3® Coulter Counter available from Beckman Coulter.

Example I
Resin A, a crystalline copoly- (ethylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane) resin derived from ethylene glycol, dodecanedioic acid and carbinol (hydroxyl) terminated polydimethylsiloxane, is as follows: Prepared.

  In a 2 liter Buchi reactor, 675.7 g dodecanedioic acid, 200 g ethylene glycol, and Gelest Inc. 250 g carbinol-terminated polydimethylsiloxane having a viscosity of about 50 to about 65 centistokes available as DMS-16 from 1 g and 1 g of butylstanoic acid catalyst FASCAT® 4100 available from Elf Atochem. . The resulting mixture was slowly heated to 225 ° C. over 3 hours and then maintained at 225 ° C. for an additional 5 hours. Next, the obtained resin is taken out into a metal container and solidified at room temperature of 20 ° C. to 25 ° C. to obtain the following crystalline copoly- (ethylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane) resin. It was.

Here, m is 10, n is 2, R ¹ and R ² are methyl, the a segment is about 75% of the resin, and the b segment is about 25% of the resin.

The resin prepared above had a melting point temperature (T _m ) of 77.9 ° C., a recrystallization temperature (T _c ) of 55.5 ° C., and a heat of fusion of 66 joules / gram measured with a DuPont 910 differential scanning calorimeter. The weight average molecular weight of the resin prepared above was 18.4 kilo (k) as measured on a Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™) system using polystyrene standards. The number average molecular weight of the resin prepared above is 7.8 kg measured on a Waters (R) ACQUITY (R) Advanced Polymer Chromatography (TM) (APC (TM)) system using polystyrene standards. Dalton. See Table 1 below.

  The crystalline resin emulsion prepared above was formed by dissolving 100 g of this resin in 100 g of methyl ethyl ketone and 3 g of isopropanol. Next, the obtained mixture was heated to 40 ° C. with stirring, and 5.5 g (10% aqueous solution) of ammonium hydroxide was added dropwise to the obtained mixture, and then 200 g of water was added dropwise over 30 minutes. The resulting dispersion was then heated to 80 ° C., methyl ethyl ketone was removed by distillation, and 38.03 wt% crystalline copoly- (ethylene dodecanoate) -copoly- (3-propyl-) dispersed in water. Resin A which is a (dimethylsiloxane) resin was obtained. Crystalline copoly- (ethylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane) resin emulsion particles were 165 nanometer size diameter as measured by Nanotrac® U2275E particle size analyzer. .

Example II
Resin B, a crystalline copoly- (nonylene-dodecanoic acid) -copoly- (3-propyl-dimethylsiloxane) resin derived from 1,9-nonanediol, dodecanedioic acid and carbinol (hydroxyl) terminated polydimethylsiloxane, Prepared as follows.

  In a 2 liter Buchi reactor, 564 g dodecanedioic acid, 375.8 g 1,9-nonanediol, Gelest Inc. 150 g carbinol-terminated polydimethylsiloxane having a viscosity of about 50 to about 65 centistokes available as DMS-16 from 1 g and 1 g of butylstannoic acid catalyst FASCAT® 4100 available from Elf Atochem. . The resulting mixture was slowly heated to 225 ° C. over 3 hours and then maintained at 225 ° C. for an additional 5 hours. The obtained resin was taken out into a metal container and solidified at room temperature to obtain 35% by weight of resin B which is the following crystalline copoly- (nonylene-dodecanoic acid) -copoly- (3-propyl-dimethylsiloxane).

Where m is equal to 10, n is equal to 9, R ¹ and R ² are methyl, a and b represent random segments of the resin, the a segment is about 85% of the resin, and the b segment is About 15% of the resin.

The crystalline copoly- (nonylene-dodecanoic acid) -copoly- (3-propyl-dimethylsiloxane) resin prepared above has a melting point temperature (T _m ) of 77.1 ° C. and a recrystallization temperature (T _c ) of 54. 0.8 ° C. and the heat of fusion was 105 joules / gram, all of which were measured with a DuPont 910 differential scanning calorimeter. The weight average molecular weight of this resin is 23.6 kilodaltons as measured with a Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™) system using polystyrene standards. The number average molecular weight of was 13.6 kilodaltons as measured on a Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™) system using polystyrene standards. See Table 1 below.

  The crystalline resin B emulsion prepared above was prepared by dissolving 100 g of this resin in 100 g of methyl ethyl ketone and 3 g of isopropanol. The resulting mixture was heated to 40 ° C. with stirring, 5.5 g of ammonium hydroxide (10% aqueous solution) was added dropwise to the mixture, and then 200 g of water was added dropwise over 30 minutes. The resulting dispersion was then heated to 80 ° C. and methyl ethyl ketone was removed by distillation to give 35% by weight of crystalline copoly- (nonylene-dodecanoate) -copoly- (3-propyl-dimethylsiloxane) Resin B Was obtained in water.

  Crystalline copolyester copoly- (nonylene-dodecanoic acid) -copoly- (3-propyl-dimethylsiloxane) emulsion grains were measured using a Nanotrac® U2275E particle size analyzer with a size diameter of 171 nanometers. there were.

Example III
Amorphous polyester resin terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- derived from propoxylated bisphenol A, terephthalic acid, dodecenyl succinic acid and fumaric acid Resin C, which is (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate), was prepared as follows.

  A 1 liter Buchi reactor equipped with a mechanical stirrer, bottom drain valve, and distillation apparatus was charged with propoxylated bisphenol A (433.8 g, 53.25 wt%), terephthalic acid (109.4 g, 23.4 wt%). ), Dodecenyl succinic anhydride (DDSA) (100.5 g, 16 wt%), trimellitic anhydride (9.5 g, 2.33 wt%) and catalyst FASCAT® 4100 butylstanoic acid (2.5 g) And heated to 230 ° C. over 2-3 hours and maintained at 230 ° C.-235 ° C. under nitrogen for an additional 8 hours. During this time, water was collected in the distillation receiver. The resulting mixture was then heated at 225 ° C. and after applying a vacuum (2-3 mm Hg) for 6 hours, an acid number of 4.19 mg / g KOH having a solid softening point of 101.4 ° C. was obtained. The resulting mixture was heated at 190 ° C., then fumaric acid (16.7 g, 3.9 wt%) and hydroquinone (0.5 g) were added, heated to 203 ° C. over 3 hours, 14.2 mg / g Vacuum was applied for a further 3 hours until a softening point of 120.2 ° C. with an acid number of KOH was reached. The reaction product terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol) (A-trimellitate) resin was put into a container and cooled to room temperature. When measured with a DuPont 910 differential scanning calorimeter, a glass transition temperature (Tg) of 59.4 ° C. was obtained for this resin. The weight average molecular weight of this resin is 19.7 kilo (k) Daltons using polystyrene standards and the number average molecular weight is Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™). ) It was 4.67 kilodaltons as measured by the system using polystyrene standards.

  Amorphous polyester resin terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate derived from propoxylated bisphenol A, terephthalic acid, dodecenyl succinic acid and fumaric acid resin Resin C which is) -terpoly- (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate) was produced by dissolving 100 g of this resin in 100 g of methyl ethyl ketone and 3 g of isopropanol. The resulting mixture was then heated to 40 ° C. with stirring, 5.5 g of ammonium hydroxide (10% aqueous solution) was added dropwise to the mixture, and 200 g of water was added dropwise over 30 minutes. Subsequently, the obtained dispersion was heated to 80 ° C., methyl ethyl ketone was removed by distillation, and terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinic acid ester) as resin C A dispersion of amorphous polyester resin of) -terpoly- (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate) was obtained in water. The resulting amorphous polyester emulsion grains were measured using a Nanotrac® U2275E particle size analyzer and had a size diameter of 155 nanometers.

Example IV
Amorphous poly (styrene-acrylate) composed of polymer particles formed from emulsion polymerization of 81 wt% styrene, 19 wt% n-butyl acrylate, and 1.5 wt% beta-carboxyethyl acrylate (β-CEA) Resin D, which is a resin, was prepared as follows.

  Preparation of Calfax surfactant solution: 0.334 kg of CALFAX® DB-45 (anionic emulsifier sodium dodecyl diphenyloxide disulfonate available from Pilot Chemical Company, 45% active), and 87.23 kg of dehydrated Ionized water was placed in a stainless steel 100 gallon reactor and mixed at 110 rpm. The reactor was fitted with a condenser and purged with 10 standard cubic feet of nitrogen per hour while heating to 75 ° C and holding at a controlled rate.

  Preparation of emulsified monomer: Apart from the 45 gallon plastic drum, 1.89 kg of CALFAX® DB-45 and 46.73 kg of deionized water were combined to obtain a surfactant solution. Separately in a 50 gallon reactor, 81.1 kg styrene, 19.02 kg butyl acrylate, 1.05 kg β-CEA, 1.37 kg 1-dodecanethiol (DDT), and 0.350 kg 1 , 10-decanediol diacrylate (ADOD) was mixed to prepare a monomer emulsion. The resulting surfactant solution was then transferred to a 50 gallon reactor containing the monomer emulsion prepared above with stirring at 150 rpm. The surfactant solution and the monomer emulsion were mixed for 5 minutes, then the mixing was stopped for 3 minutes, and this mixing / standing was repeated twice to prepare an emulsified monomer aqueous solution.

  Separately, in a 5 gallon can, 1.50 kg of ammonium persulfate initiator was dissolved in 13.91 kg of deionized water.

  7.60 kg (5% seed) of the emulsified aqueous monomer solution prepared above was added to the reactor containing the heated CALFAX® surfactant solution to form a seed. After 20 minutes, the addition of the ammonium persulfate initiator solution was started and placed in the reactor over 23.5 minutes followed by the addition of 1 kg of deionized water.

  Monomer Feed Reaction: After 20 minutes, the remaining monomer emulsion was added to a 100 gallon reactor over two aliquots of Feed # 1 and Feed # 2. Feed # 1 was added to the reactor over 120 minutes to equal 72.2 kg of emulsified monomer, followed by 1.2 kg of deionized water (chaser). To the remaining monomer emulsion (Feed # 2), 0.63 kg of 1-dodecanethiol (DDT) was added and fed to the reactor over 90 minutes. At this point, the rpm was increased to 120 and an additional 2.3 kg of deionized water was added to the reactor to remove the emulsified monomer from the pump line. The reactor was held at 75 ° C. for 60 minutes. The condenser was stopped at 75 ° C. after 1 hour of reaction and excess monomer was bubbled out of the reactor for 120 minutes before cooling to room temperature.

  Next, the white non-viscous liquid obtained as described above was discharged to two plastic drums with lids after the temperature had settled to room temperature. The particle size was then measured with a Nanotrac® U2275E particle size analyzer. A narrow particle size was achieved with a particle size of 188 nanometers ± 60 nanometers. After drying the sample with a lyophilizer, a glass transition temperature (Tg) of 55.3 ° C. was obtained and evaluated with a DuPont 910 differential scanning calorimeter. The weight average molecular weight is 24.5 kilodaltons as measured on a Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™) system using polystyrene standards, and the number average molecular weight is It was 8.97 kilodaltons as measured on a Waters® ACQUITY® Advanced Polymer Chromatography ™ (APC ™) system using polystyrene standards. Resin D, which was the resulting poly (styrene-acrylate) resin latex, was obtained as an aqueous dispersion containing 40.75% by weight in water.

Example V
Resin B (35% by weight of total resin), which was the crystalline copoly- (nonylene-dodecanoic acid) -copoly- (3-propyl-dimethylsiloxane) resin of Example II prepared above, and the example prepared above Amorphous polyester resin terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly from III propoxylated bisphenol A, terephthalic acid, dodecenyl succinic acid and fumaric acid -(Propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate) core of resin C (35% by weight of total resin) and the amorphous poly (styrene of Example IV prepared above. -Acrylate) resin Composed of resin D (30% by weight of the total resin) is included in the shell covering the core, was prepared cold pressure fixing toner cyan.

  In a 2 liter glass reactor equipped with an overhead stirrer, 39.26 g of PB15: 3 dispersion (15.27 wt%) and 89.41 g of crystalline copoly- (nonylene-dodecanoic acid) -copoly- Resin B which is (3-propyl-dimethylsiloxane) and 84.80 g terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated) Resin C which is bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate) was added. The pH of the resulting mixture was adjusted to 3.14 by addition of a 0.3 molar aqueous nitric acid solution and then homogenized at 4,000 rpm using an IKA ultra turrax mixer. To the resulting mixture, 23.89 g of aluminum sulfate solution was added dropwise while continuously homogenizing. After homogenization, the resulting mixture was stirred at 200 rpm and heated from room temperature to 47 ° C. at a rate of 1 ° C./min. The particle size was monitored using a Coulter Counter ™ analyzer until the core particles reached a volume average particle size of 5.36 microns (μm). Next, 74.36 g of an amorphous styrene acrylate (resin D) latex was added as a shell material to obtain core-shell structured particles having an average size of 6.34 microns. Thereafter, the pH of the reaction slurry was raised to 7.8 using 2.37 g EDTA (39 wt% in water) to freeze the toner growth. After freezing, the reaction mixture was heated to 70 ° C. and the pH of the mixture was lowered to 6 by adding 29.39 g of 0.3 molar aqueous nitric acid. The reaction temperature was then raised to 75 ° C. and maintained at this temperature for a total of 90 minutes for coalescence, then cooled to room temperature, separated with a sieve (25 μm, filter), washed and lyophilized. The resulting core-shell toner exhibited a final particle size of 6.08 microns, a geometric size distribution (GSD) of 1.20 (volume) and 1.22 (number), and a circularity of 0.975.

  A number of cyan cold pressure fixing toners were prepared according to the procedure of Example V, and both the core and shell resin compositions were varied as shown in Table 2. Here, the particle size is measured with a Coulter counter, the GSD v / n is measured with a measuring device such as a Coulter counter or a Multisizer 3 (registered trademark) Coulter Counter available from Beckman Coulter, and the circularity is measured with a Beckman. Measurements were taken on a Multisizer 3® Coulter Counter available from Coulter.

Cold Pressure Fixing A laboratory cold pressure fixing device has a process speed of 243 mm / s, a variable nip pressure load area of 1,000 psi (6.9 MPa, megapascal) and 1,500 psi (10.3 MPa), and a roll contact length. Used at a thickness of 70 mm. The pressure was maintained at a constant 5 kg / cm ² (82 lb / in ² ). Toner images were generated on paper using a Xerox Corporation 800 printer with fusing fixation disabled. The resulting unfused print was then subjected to the laboratory cold pressure fixing device. Taber Linear Abraser (Model 5700) was then used with a commercially available Clock cross attachment to evaluate image durability. The image was rubbed at 10 cycles / min and then 60 cycles / min. All of the toners in Table 2 above showed excellent toner fixation on paper, and during the test with Taber Linear Abraser (Model 5700) there was no or minimal transfer of the toner image to the Clock cloth.

  The cold pressure fixing performance of the toner prepared in Table 2 above was evaluated using a modified Adirondack Machine Corporation pressure device for the generated unfused image, and the device was composed of two metal rolls ( The top roll is coated with TEFLON® and machined so that the width of the high pressure zone through the nip of the metal roll system is 70 mm. The process speed of the cold pressure fixing device was set to 240 mm / s and the load between the two rolls was applied by compressing a metal spring to obtain the desired nip pressure. Two variable nip pressure load areas of 1,000 psi (6.9 MPa) and 1,500 psi (10.3 MPa) were applied to each toner sample. The unfused print was then subjected to the cold pressure fixing described above, and the image durability was then evaluated by Taber's standard friction fixing procedure. The halftone pattern of the fused print was rubbed using a Taber Linear Abrader fitted with a Clock cloth. During the test, a 500 g load was used in two cycles of rubbing the pattern. After physically rubbing the pattern, the Clock cloth was removed from the Taber Linear Abrader, and the average optical density of the toner transferred to the cloth was measured with a Gretag / Macbeth Transmission Densitometer. The image fixing was then ranked on a scale of 1-5, where 1 is poor fixing and 5 is good fixing (black bar is 1,000 psi, red bar is 1500 psi). See the bar graph below showing the relative adhesion values of selected samples.

[table]

  In addition, pen offset, which refers to an image that flips to another page when the image is pressed with a pen, achieves performance with many of the cold-fixing toners in Table 2; A higher value was obtained indicating

  The pen offset, which determines toner adhesion to the paper, was then terminated for each test print placed face down separately on a blank area of Xerox Corporation Bold paper. The amount of toner transferred from the printed material to the white paper indicates how well the toner adheres to the page. A 6 mm diameter stainless steel ball attached to the holder was placed in contact with the back side of the test print while applying a load. Three different loads (1N, 2N and 5N, force units Newton) were used over a length of 40 mm and 20 mm / sec. For testing purposes, a CSM tribometer available from Rtec Instruments was used.

Claims (10)

  A cold-pressing toner composition comprising a colorant, a core comprising a crystalline copolyester-copolydimethylsiloxane resin and an amorphous resin, and a polymer shell covering the core. The crystalline copolyester-copolydimethylsiloxane resin is represented by the following formula / structure:

Wherein R ¹ and R ² are methyl, a is a number from 1 to about 1,000, b is a number from 1 to about 100, m is a number from 2 to about 12, and n is 0 or n is a number from 2 to about 12, p is a number from 5 to about 1,000, and a and b represent random segments of the crystalline copolyester-copolydimethylsiloxane. The toner according to claim 1, wherein a sum of the a and the b is about 100%.   The a is a number from about 300 to about 700, the b is a number from about 50 to about 75, the m is a number from about 6 to about 10, and the n is a number from about 4 to about 10. The toner of claim 2, wherein p is a number from 325 to about 725.   The crystalline copolyester-copolydimethylsiloxane resin is copoly (hexylene dodecanoate) -copoly- (3-propyl-dimethylsiloxane), copoly (butylene decanoate) -copoly- (3-propyl-dimethylsiloxane). Copoly- (ethylene sebacate) -copoly- (3-propyl-dimethylsiloxane), copoly- (butylene sebacate) -copoly- (3-propyl-dimethylsiloxane), copoly- (butylene decanoate) -copoly- (3-propyl-dimethylsiloxane), copoly- (ethylenedodecanoate) -copoly- (3-propyl-dimethylsiloxane), and copoly- (nonylenedodecanoate) -copoly- (3-propyl-dimethylsiloxane) Selected from the group consisting of: Toner of the mounting.   The amorphous resin is terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate), terpoly- (propoxyl). Bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxyl) Bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate), poly (pro Xylated bisphenol A-cofumarate), copoly (propoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate), copoly (ethoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol- The toner of claim 1, wherein the toner is selected from the group consisting of fumarate) and copoly (butoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate). A cold-fixing toner comprising a core comprising a colorant, wax, optional additives, a copolyester-copolydimethylsiloxane and amorphous resin mixture, and a shell comprising a polymer and covering the core. The copolyester-copolydimethylsiloxane is represented by the following formula / structure:

Wherein R ¹ and R ² are methyl, a is a number from 1 to about 1,000, b is a number from 1 to about 100, m is a number from 2 to about 12, and n is A number from 0 to about 12, p is a number from 5 to about 1,000, the a and b represent random segments of the copolyester-copolydimethylsiloxane, and the sum of a and b is about 100% cold fixing toner.   The amorphous resin is terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate), and terpoly- (propoxy). Bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxy) Bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate) And the shell polymer is terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate), and terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate)- terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol - trimellitate) is selected from the group consisting of a cold pressure fixing toner according to claim 6. Colorants, waxes,

A copolyester-copolydimethylsiloxane crystalline resin represented by:
Wherein R ¹ and R ² are methyl, a is a number from 1 to about 1,000, b is a number from 1 to about 100, m is a number from 6 to about 10, and n is A copolyester-copolydimethyl having a number from 4 to about 10 and p being a number from 5 to about 1,000, wherein said a and said b represent random segments of said copolyester-copolydimethylsiloxane crystalline resin. Siloxane crystalline resin, terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) terpoly- (propoxylated bisphenol A-fumarate), terpoly- (propoxylated bisphenol) A-terephthalate) -terpoly- (propoxylated bisphenol -Dodecenyl succinate) -terpoly-(ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A) -Trimellitate), poly (propoxylated bisphenol-A-coumarate), copoly (propoxylated bisphenol-fumarate) -copoly (trimethylolpropoxylated-bisphenol-fumarate), copoly (ethoxylated bisphenol-fumarate) -copoly ( Trimethylolpropoxylated-bisphenol-fumarate), copoly (butoxylated bisphenol-fumarate) -copoly (to Amorphous selected from the group consisting of limethylolpropoxylated-bisphenol-fumarate) and copoly (propoxylated 1,4-diphenol-fumarate) -copoly (glycerinoxylated-diphenol-fumarate) A cold-pressure fixing toner composition comprising: a core containing a mixture of a resin; and a shell surrounding the core, the shell selected from the group consisting of styrene acrylate and the amorphous resin.   The amorphous resin for the shell is terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate), and terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) -terpoly- (ethoxylated bisphenol A-dodecenyl succinate)- terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate) It is selected from the group consisting of chromatography g) The toner according to claim 8.   The copolyester-copolydimethylsiloxane crystalline resin is present in an amount of about 10% to about 75% by weight of the toner and the amorphous resin is present in an amount of about 25% to about 50% by weight of the toner. The toner according to claim 8.